SK7742002A3 - Method for producing fatty acid alkyl esters - Google Patents
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- SK7742002A3 SK7742002A3 SK774-2002A SK7742002A SK7742002A3 SK 7742002 A3 SK7742002 A3 SK 7742002A3 SK 7742002 A SK7742002 A SK 7742002A SK 7742002 A3 SK7742002 A3 SK 7742002A3
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
- C11C3/10—Ester interchange
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
Abstract
Description
Vynález sa týka spôsobu prípravy alkylesterov mastných kyselín transesterifikáciou, najmä katalytickou transesterifikáciou, zmesi triglyceridov a mastných kyselín, pričom z reakčnej zmesi, v ktorej sa transesterifikácia uskutočňuje, sú vytvorené esterová fáza obsahujúca alkylestery mastných kyselín a glycerínová fáza obsahujúca mastné kyseliny, ktoré sú od seba navzájom oddelené, a mastné kyseliny sú oddeľované z glycerínovej fáze, čím je tvorená fáza mastných kyselín obsahujúca mastné kyseliny, a tieto mastné kyseliny sú esterifikované príslušným alkoholom.The invention relates to a process for the preparation of alkyl esters of fatty acids by transesterification, in particular catalytic transesterification, of a mixture of triglycerides and fatty acids, wherein the reaction mixture in which the transesterification is carried out forms an ester phase containing fatty acid alkyl esters and glycerin phase containing fatty acids. separated from each other, and the fatty acids are separated from the glycerin phase, thereby forming a fatty acid phase containing fatty acids, and these fatty acids are esterified with an appropriate alcohol.
Doterajší stav technikyBACKGROUND OF THE INVENTION
Triglyceridy, estery vytvorené z nasýtených a/alebo nenasýtených vyšších mastných kyselín a glycerínu sa chápu ako ako látky na účel tejto špecifikácie a patentových nárokov. Takýmito estermi sú napr. tuky rastlinného alebo živočíšneho pôvodu a rovnako aj opotrebované pokrmové oleje a odpadové tuky. Mnohé tuky prírodného pôvodu však obsahujú aj voľné mastné kyseliny vo väčšom či menšom rozsahu. Tieto tuky sú potom zmesou triglyceridov a voľných mastných kyselín, pričom hlavnou súčasťou tejto zmesi sú zvyčajne triglyceridy.Triglycerides, esters formed from saturated and / or unsaturated higher fatty acids and glycerin are understood to be substances for the purpose of this specification and the claims. Such esters are e.g. fats of vegetable or animal origin, as well as worn edible oils and waste fats. However, many fats of natural origin also contain free fatty acids to a greater or lesser extent. These fats are then a mixture of triglycerides and free fatty acids, the main part of which is usually triglycerides.
Pod pojmom transesterifikácia je potrebné rozumieť alkoholýzu triglyceridov, t.j. reakciu s alkoholmi, najmä metanolom a etanolom, pričom monoestery mastných kyselín aj glycerínu sú tvorené cez prechodné produkty di- a monoglyceridy.By transesterification is meant the triglyceride alcoholysis, i. by reaction with alcohols, in particular methanol and ethanol, wherein both fatty acid and glycerin monoesters are formed by the di- and monoglycerides via the intermediate products.
Estery mastných kyselín, najmä metylestery, sú dôležitými medziproduktami v chémii olejov. Len v Európe sa ročne vyrába 200.000 tonFatty acid esters, especially methyl esters, are important intermediates in oil chemistry. In Europe alone, 200,000 tonnes are produced annually
-2metylesterov rastlinných olejov ako suroviny hlavne pre tenzidy. Okrem toho získava metylester mastných kyselín stále väčší význam ako náhrada za Dieselovo palivo (motorovú naftu).-2-methyl esters of vegetable oils as raw materials mainly for surfactants. In addition, the fatty acid methyl ester is becoming increasingly important as a substitute for diesel fuel.
Ako katalyzátory pre transesterifikáciu sa môžu použiť bázické katalyzátory (alkalické hydroxidy, alkoholáty, oxidy, uhličitany, anexy), kyslé katalyzátory (minerálne kyseliny, p-toluénsulfónová kyselina, bórtrifluorid, katex) a enzýmy (lipázy). Prednostne sa v súčasnosti používajú katalyzátory, ktoré sú rozpustné v reakčnej zmesi. Tie tvoria homogénnu zmes a zaručujú rýchle transformačné alebo reakčné rýchlosti a mierne reakčné podmienky. Najčastejšie používanými homogénnymi katalyzátormi sú hydroxid sodný a draselný, ako aj metylát sodný, ktoré sa po rozpustení v alkohole primiešavajú do rastlinného oleja. Takýto spôsob je známy z AT-B 386 222. Kyslá katalýza vyžaduje vyššie reakčné teploty a tlaky a nákladnejšie vykonanie reakcie. Kyslá transesterifikácia je známa z FR-A-85 02340.As catalysts for transesterification, basic catalysts (alkali hydroxides, alcoholates, oxides, carbonates, anion exchangers), acid catalysts (mineral acids, p-toluenesulfonic acid, boron trifluoride, cation exchanger) and enzymes (lipases) can be used. Preference is given to using catalysts which are soluble in the reaction mixture. These form a homogeneous mixture and guarantee rapid transformation or reaction rates and mild reaction conditions. The most commonly used homogeneous catalysts are sodium and potassium hydroxides, as well as sodium methylate, which, when dissolved in an alcohol, are mixed into the vegetable oil. Such a process is known from AT-B 386 222. Acid catalysis requires higher reaction temperatures and pressures and more costly to carry out the reaction. Acid transesterification is known from FR-A-85 02340.
Transesterifikácia s bázickou katalýzou sa uskutočňuje bez použitia rozpúšťadla. Reakcia začína dvojfázovým systémom z triglyceridu a alkoholu; ale postupom reakcie a vznikom esteru sa tvorí homogénna fáza, ktorá sa vznikom a odlučovaním glycerínu opäť rozpadáva na dve fázy.Transesterification with basic catalysis is carried out without the use of a solvent. The reaction starts with a two-phase system of triglyceride and alcohol; but by the process of reaction and ester formation a homogeneous phase is formed which again breaks down into two phases by the formation and separation of glycerin.
Pri alkoholýze triglyceridov s cieľom prípravy esterov mastných kyselín s jednomocnými alkoholmi vzniká ako vedľajší produkt fáza bohatá na glycerín. Táto fáza ďalej obsahuje mastné kyseliny, soli mastných kyselín a estery mastných kyselín. Aby sa tieto zlúčeniny mastných kyselín oddelili z glycerínovej fázy, sa obvykle spracovávajú príslušnými kyselinami. Týmto spracovávaním sa zo solí mastných kyselín uvoľňujú dané mastné kyseliny. Mastné kyseliny, ako aj estery týchto kyselín, nie sú samotné s glycerínom miešateľné a sedimentujú preto ako vlastná fáza z glycerínovej fáze. Táto fáza je označovaná ako fáza mastných kyselín.In the alcoholysis of triglycerides to prepare fatty acid esters of monovalent alcohols, a glycerin-rich phase is formed as a by-product. This phase further comprises fatty acids, fatty acid salts and fatty acid esters. In order to separate these fatty acid compounds from the glycerol phase, they are usually treated with the appropriate acids. This treatment releases the fatty acids from the fatty acid salts. Fatty acids, as well as esters of these acids, are not miscible with glycerine alone and therefore sediment as a phase from the glycerin phase. This phase is referred to as the fatty acid phase.
-3Spôsob na počiatku uvedeného druhu možno prevziať z EP-A-0 708 813. Tento už známy spôsob zhodnocuje fázu mastných kyselín, keď v tejto fáze obsiahnuté mastné kyseliny sa esterifikujú príslušným alkoholom a získané alkylestery mastných kyselín sa pridajú k inej reakčnej zmesi, v ktorej bola práve uskutočnená príslušná transesterifikácia.The method of the initially mentioned kind can be taken from EP-A-0 708 813. This already known process evaluates the fatty acid phase, when the fatty acids contained therein are esterified with the corresponding alcohol and the obtained fatty acid alkyl esters are added to another reaction mixture, in whose transesterification has just been performed.
Ak už bolo uvedené, obsahujú tuky prírodného pôvodu tiež voľné mastné kyseliny v rozdielnom rozsahu. Čím vyšší je tento podiel voľných mastných kyselín, tým menej triglyceridu je k dispozícii ako suroviny pre transesterifikáciu. Naopak výťažok alkylesterov mastných kyselín sa môže zvýšiť, ak sú voľné mastné kyseliny esterifikované v samostatnom kroku, ako to bolo vo vyššie uvedenom EP-A-0 708 813.As already mentioned, fats of natural origin also contain free fatty acids to different extents. The higher this proportion of free fatty acids, the less triglyceride is available as raw material for transesterification. Conversely, the yield of alkyl esters of fatty acids may be increased if the free fatty acids are esterified in a separate step, as in the above-mentioned EP-A-0 708 813.
Z Oleagineuxu, zv. 40, č. 3, str. 148-151 (1985), je známa esterifikácia voľných mastných kyselín obsiahnutých vo fáze mastných kyselín (na etylester) pomocou zmesi (získanej po príprave tukov extrakciou z rozpúšťadiel a tukov) obsahujúcej etanol na etylester, použitím kyseliny sírovej ako katalyzátora, neutralizácia kyseliny sírovej oxidom vápenatým (CaO), odfiltrovanie vytvoreného síranu vápenatého, zmiešanie získaného esteru s transesterifikačným katalyzátorom a transesterifikácia príslušnej zmesi bohatej na olej touto zmesou. Na olej bohatá zmes sa získa pri extrakcii suroviny obsahujúcej olej alebo tuk a je tak zmesou extrakčného činidla a transesterifikovaného triglyceridu. Tento spôsob je veľmi nákladný a nie je vhodný na transesterifikáciu surovín obsahujúcich olej a ktoré obsahujú voľné mastné kyseliny.From Oleagineux, Vol. 40, no. 3, p. 148-151 (1985), it is known to esterify the free fatty acids contained in the fatty acid phase (to the ethyl ester) by means of a mixture (obtained after the preparation of fats by extraction from solvents and fats) containing ethanol to the ethyl ester using sulfuric acid as a catalyst. calcium (CaO), filtering out the formed calcium sulfate, mixing the obtained ester with the transesterification catalyst, and transesterifying the respective oil-rich mixture with the mixture. The oil-rich mixture is obtained by extracting an oil or fat-containing feedstock and is thus a mixture of an extraction agent and a transesterified triglyceride. This process is very expensive and is not suitable for transesterification of oil-containing feedstocks containing free fatty acids.
Podstata vynálezuSUMMARY OF THE INVENTION
Tento vynález uvádza a dáva si za úlohu poskytnúť spôsob na počiatku opísaného druhu, podľa ktorého daná fáza mastných kyselín sa môže spracovávať v nespracovanom stave, t.j. bez čistenia a odstraňovania kyselinyIt is an object of the present invention to provide a process of the kind initially described according to which a given fatty acid phase can be processed in an unprocessed state, i. without purification and acid removal
-4sírovej, a podľa ktorého môžu byť aj suroviny, ktoré majú väčší obsah voľných mastných kyselín, transesterifikované.-4-sulfuric acid, and according to which the raw materials having a higher free fatty acid content can also be transesterified.
Daný spôsob podľa tohto vynálezu sa vyznačuje tým, že fáza mastných kyselín sa mieša s ďalšou zmesou triglyceridov a mastných kyselín a mastné kyseliny obsiahnuté v získanej zmesi sa esterifikujú určitým alkoholom, pričom sa získa esterifikačná zmes, ktorá obsahuje triglyceridy a alkylestery mastných kyselín, a táto esterifikačná zmes sa transesterifikuje alkoholom pri vzniku ďalších alkylesterov mastných kyselín.The process according to the invention is characterized in that the fatty acid phase is mixed with another mixture of triglycerides and fatty acids and the fatty acids contained in the obtained mixture are esterified with a certain alcohol to obtain an esterification mixture comprising triglycerides and alkyl esters of fatty acids, and the esterification mixture is transesterified with an alcohol to form additional alkyl esters of fatty acids.
Podľa spôsobu tohto vynálezu sa mastné kyseliny obsiahnuté v transesterifikovanom tuku alebo oleji (tzn. zmes triglyceridov a mastných kyselín) pred vlastnou transesterifikáciou esterifikujú príslušným alkoholom, pričom táto esterifikácia sa uskutočňuje za prítomnosti fáze mastných kyselín z predchádzajúcej transesterifikácie, takže jednak mastné kyseliny obsiahnuté v transesterifikovanom tuku, tak aj mastné kyseliny obsiahnuté v pridanej fáze mastných kyselín, sa esterifikujú.According to the method of the invention, the fatty acids contained in the transesterified fat or oil (i.e., a mixture of triglycerides and fatty acids) are esterified with the corresponding alcohol prior to the transesterification, the esterification being carried out in the presence of the fatty acid phase of the previous transesterification. The fatty acids contained in the added fatty acid phase are esterified.
Fáza mastných kyselín z predošlej transesterifikácie sa nemusí čistiť a môže sa ako taká, tzn. aj s nadbytočným metanolom, pridávať k danému tuku.The fatty acid phase of the previous transesterification need not be purified and can be treated as such, i.e.. even with excess methanol, add to that fat.
Ak tuk obsahuje skutočne veľký podiel voľných mastných kyselín, esterifikačná zmes získaná po prvej esterifikácii môže byť esterifikovaná príslušným alkoholom minimálne ešte raz pred transesterifikáciou. Týmto spôsobom sa môže obsah voľných mastných kyselín stupňovité zmenšovať, takže sa umožní výťažok alkylesterov mastných kyselín 100 %.If the fat actually contains a large proportion of free fatty acids, the esterification mixture obtained after the first esterification can be esterified with the appropriate alcohol at least once before transesterification. In this way, the free fatty acid content may be reduced in steps, so that a yield of alkyl fatty acid esters of 100% is possible.
Spôsob podľa vynálezu je charakterizovaný tým, že zmes triglyceridov a mastných kyselín zmiešaná s fázou mastných kyselín má obsah mastných kyselín najmenej 5 % hmotn., alebo najmenej 10 % hmotn.The process according to the invention is characterized in that the mixture of triglycerides and fatty acids mixed with the fatty acid phase has a fatty acid content of at least 5% by weight, or at least 10% by weight.
-5Esterifikácia sa prednostne uskutočňuje počas kyslej katalýzy a transesterifikácia sa prednostne uskutočňuje počas alkalické katalýzy.The esterification is preferably performed during acid catalysis and the transesterification is preferably performed during alkaline catalysis.
Pri spôsobe podľa tohto vynálezu sa ako alkohol na transesterifikáciu a esterifikáciu používajú najmä metanol alebo etanol.In the process according to the invention, in particular methanol or ethanol are used as alcohol for transesterification and esterification.
Spôsob a forma uskutočnenia tohto vynálezu sú bližšie opísané v nasledujúcom príklade.The method and embodiment of the invention are described in more detail in the following example.
Príklad uskutočnenia vynálezuDETAILED DESCRIPTION OF THE INVENTION
1. Esterifikácia1. Esterification
1000 g opotrebovaného pokrmového oleja so 7, 15 % obsahom voľných mastných kyselín sa najprv zmiešalo so 100 g metanolu a 7,0 g H2SO4 (98 %) s cieľom esterifikácie a 2 hodiny varilo pri spätnom toku (refluxované). Zmes sa premiestnila do oddeľujúcej nádoby a rozdelila sa na vodnú fázu (51,6 g) a olejovú fázu (1045,0 g).1000 g of spent cooking oil with a 7, 15% free fatty acid content was first mixed with 100 g of methanol and 7.0 g of H2SO4 (98%) for esterification and refluxed for 2 hours. The mixture was transferred to a separating vessel and partitioned into an aqueous phase (51.6 g) and an oil phase (1045.0 g).
2. Transesterifikácia2. Transesterification
Olejová fáza sa podrobila dvojstupňovej alkalickej transesterifikácii podľa spôsobu opísanom v AT-B 386.222. Olejová fáza sa pritom zmiešala spolu so 192,2 g metanolu a 12,19 g KOH a vzniknutá glycerínová fáza sa po každom stupni oddelila. Vytvorená esterová fáza (917,8 g) sa demetanolizovala v Rotavapore (40,8 g), a získalo sa 877,0 g metylesteru mastných kyselín.The oil phase was subjected to a two-step alkaline transesterification according to the method described in AT-B 386.222. The oil phase was mixed with 192.2 g of methanol and 12.19 g of KOH, and the resulting glycerol phase was separated after each step. The ester phase formed (917.8 g) was demethanolized in Rotavapore (40.8 g), yielding 877.0 g of fatty acid methyl ester.
3. Vznik fáze mastných kyselín3. Formation of fatty acid phase
Obe glycerínové fáze (328, 1 g), spätne získané z transesterifikácie, pridaním 12,0 g H2SO4 dosiahli hodnotu približne 3 pH. Týmto okyslením sa vytvorili z draselných mydiel prítomných v glycerínovej fáze voľné mastné kyseliny a draselná soľ ako pevná fáza. Vzniknutá zmes sa filtrovala a filtrát saBoth glycerine phases (328, 1 g) recovered from transesterification reached about 3 pH by addition of 12.0 g H 2 SO 4 . By this acidification, free fatty acids and the potassium salt as solid phase were formed from the potassium soaps present in the glycerol phase. The resulting mixture was filtered and the filtrate was filtered
-6premiestnil do oddeľujúcej nádoby. Po oddelení fáz vznikli nasledovné množstvá: fáza mastných kyselín 103,5 g, glycerínová fáza 200,2 g, filtračný zvyšok 32,8 g.-6 moved to a separating vessel. After phase separation, the following amounts were obtained: fatty acid phase 103.5 g, glycerin phase 200.2 g, filter residue 32.8 g.
4. Esterifikácia4. Esterification
Takto spätne získaná (regenerovaná) fáza mastných kyselín (103,5 g) sa zmiešala s 896,5 g opotrebovaného pokrmového oleja s obsahom 7, 15 % voľných mastných kyselín a táto zmes sa pre esterifikáciu refluxovala so 100 g metanolu a 7,0 g H2SO4 (98%) a varila 2 hodiny. Zmes sa premiestnila do oddeľujúcej nádoby a rozdelila sa na vodnú fázu (59,2 g) a olejovú fázu (1047,8 g). Obsah voľných mastných kyselín v oleji bol 0,98 %.The recovered (fatty acid) phase (103.5 g) was mixed with 896.5 g of wasted edible oil containing 7.15% of free fatty acids and this mixture was refluxed with 100 g of methanol and 7.0 g for esterification H 2 SO 4 (98%) and boiled for 2 hours. The mixture was transferred to a separating vessel and separated into an aqueous phase (59.2 g) and an oil phase (1047.8 g). The free fatty acid content of the oil was 0.98%.
5. T ransesterifikácia5. Transesterification
Olejová fáza sa opäť podrobila dvojstupňovej alkalickej transesterifikácii podľa spôsobu opísanom v AT-B 386.222. Olejová fáza sa pritom zmiešala spolu soThe oil phase was again subjected to a two-step alkaline transesterification according to the method described in AT-B 386.222. The oil phase was mixed with
190,8 g metanolu a 12,11 g KOH a vzniknutá glycerínová fáza sa po každom stupni oddelila. Vytvorená esterová fáza (1016,4 g) sa demetanolizovala v Rotavapore (56,3 g), pričom ako čistá esterová fáze zostalo 907,1 g.190.8 g of methanol and 12.11 g of KOH and the resulting glycerol phase was separated after each step. The ester phase formed (1016.4 g) was demethanolized in Rotavapore (56.3 g) leaving 907.1 g as the pure ester phase.
6. Vznik fáze mastných kyselín6. Formation of fatty acid phase
Glycerínové fáze z transesterifikácie (282, 1 g) sa spolu spojili a pridaním 10,1 g H2SO4 dosiahli hodnotu približne 3 pH. Vzniknutá zmes sa filtrovala a filtrát sa premiestnil do oddeľujúcej nádoby. Po oddelení fáz vznikli nasledovné množstvá: fáza mastných kyselín 97,2 g, glycerínová fáza 161,2 g, filtračný zvyšok 33,8 g.The glycerin phases from the transesterification (282, 1 g) were combined and brought to about pH 3 by addition of 10.1 g H2SO4. The resulting mixture was filtered and the filtrate was transferred to a separatory vessel. After phase separation, the following amounts were obtained: fatty acid phase 97.2 g, glycerin phase 161.2 g, filter residue 33.8 g.
Claims (7)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT0169900A ATA16992000A (en) | 2000-10-05 | 2000-10-05 | METHOD FOR PRODUCING FATTY ACID ALKYL ESTERS |
| PCT/AT2001/000320 WO2002028811A1 (en) | 2000-10-05 | 2001-10-05 | Method for producing fatty acid alkyl esters |
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| SK7742002A3 true SK7742002A3 (en) | 2003-09-11 |
| SK287690B6 SK287690B6 (en) | 2011-06-06 |
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| US (1) | US6696583B2 (en) |
| EP (1) | EP1322588B1 (en) |
| JP (1) | JP2004510044A (en) |
| CN (2) | CN1392873A (en) |
| AT (1) | ATA16992000A (en) |
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| DK (1) | DK1322588T3 (en) |
| EE (1) | EE200200289A (en) |
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| US7806945B2 (en) | 2003-01-27 | 2010-10-05 | Seneca Landlord, Llc | Production of biodiesel and glycerin from high free fatty acid feedstocks |
| US7871448B2 (en) | 2003-01-27 | 2011-01-18 | Seneca Landlord, Llc | Production of biodiesel and glycerin from high free fatty acid feedstocks |
| US20050027137A1 (en) * | 2003-07-29 | 2005-02-03 | Hooker Jeffrey D. | Apparatus and method for the production of fatty acid alkyl ester |
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| GB612667A (en) * | 1945-05-29 | 1948-11-16 | Unilever Ltd | Improvements in or relating to methods of alcoholysis of low grade fatty materials |
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2000
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- 2001-10-05 NZ NZ519001A patent/NZ519001A/en not_active IP Right Cessation
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- 2001-10-05 RU RU2002115817/04A patent/RU2287519C2/en active
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- 2001-10-05 EE EEP200200289A patent/EE200200289A/en unknown
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- 2001-10-05 AU AU91466/01A patent/AU9146601A/en not_active Abandoned
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- 2001-10-05 CA CA2392723A patent/CA2392723C/en not_active Expired - Fee Related
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| EP1322588A1 (en) | 2003-07-02 |
| HUP0204190A3 (en) | 2011-01-28 |
| HUP0204190A2 (en) | 2003-04-28 |
| ATA16992000A (en) | 2001-12-15 |
| CA2392723A1 (en) | 2002-04-11 |
| CZ20021854A3 (en) | 2002-11-13 |
| ES2593283T3 (en) | 2016-12-07 |
| CN1392873A (en) | 2003-01-22 |
| WO2002028811A1 (en) | 2002-04-11 |
| PL355294A1 (en) | 2004-04-05 |
| DK1322588T3 (en) | 2016-09-19 |
| NZ519001A (en) | 2004-10-29 |
| EE200200289A (en) | 2003-12-15 |
| EP1322588B1 (en) | 2016-06-29 |
| CZ298652B6 (en) | 2007-12-05 |
| RU2287519C2 (en) | 2006-11-20 |
| SK287690B6 (en) | 2011-06-06 |
| AU9146601A (en) | 2002-04-15 |
| CN101792388A (en) | 2010-08-04 |
| BR0107288A (en) | 2002-08-27 |
| PL206658B1 (en) | 2010-09-30 |
| LT1322588T (en) | 2016-10-10 |
| US20030004363A1 (en) | 2003-01-02 |
| ZA200203786B (en) | 2003-05-13 |
| US6696583B2 (en) | 2004-02-24 |
| JP2004510044A (en) | 2004-04-02 |
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| MM4A | Patent lapsed due to non-payment of maintenance fees |
Effective date: 20181005 |